Chitosan-containing antiperspirant cosmetic agents which are free of halides and/or hydroxy halides of aluminum and/or zirconium

ABSTRACT

The invention relates to an antiperspirant cosmetic agent which includes at least one specific chitosan and which is free of aluminum-containing compounds, in particular free of halides and/or hydroxy halides of aluminum and/or zirconium. The present invention further relates to the use of a specific chitosan and to a non-therapeutic method for reducing body perspiration. Adding or using the at least one specific chitosan ensures that the sweat gland(s) is/are effectively influenced, thus resulting in a significant reduction in underarm perspiration even in the absence of antiperspirant aluminum-containing compounds.

FIELD OF THE INVENTION

The present invention generally relates to antiperspirant cosmeticagents that are free of aluminum salts and/or free of aluminum-zirconiumsalts and that include at least one substance selected from the group ofcosmetic oils that are liquid at 20° C. and 1,013 hPa, odoroussubstances, and waxes, optionally at least one propellant, and at leastone specific chitosan. The addition of the at least one specificchitosan results in an influence on the sweat gland(s).

Furthermore, the present invention relates to a packaging unit (kit ofparts), including a cosmetic agent having at least one antiperspirantactive substance (M1) and a cosmetic agent according to the invention(M2).

The present invention also relates to the use of specific chitosans toat least partially influence the sweat gland(s).

In addition, the present invention relates to the use of a combination,including at least one substance selected from the group of cosmeticoils that are liquid at 20° C. and 1,013 hPa, odorous substances, andwaxes, optionally at least one propellant, and at least one specificchitosan, to reduce and/or prevent perspiration, particularly underarmperspiration or perspiration of other body regions. The combinationaccording to the invention includes no aluminum-containing compounds.

Finally, the present invention relates to a non-therapeutic cosmeticmethod for preventing and/or reducing the perspiration of the body,wherein an antiperspirant cosmetic agent according to the invention orthe agents (M1) and (M2) of the packaging unit according to theinvention are applied to the skin, particularly to the skin of theaxillae, and remain on the skin of the axillae for at least 1 hour,preferably for at least 2 hours, more preferably for at least 4 hours,particularly for at least 6 hours.

BACKGROUND OF THE INVENTION

The washing, cleaning, and care of one's own body is a basic human need,and modern industry is continually attempting to meet these human needsin a variety of ways. Especially important for daily hygiene is thelasting elimination or at least reduction of body odor and axillarymoisture. Numerous specific deodorizing or antiperspirant body careagents developed for use in body regions having a high density of sweatglands, particularly in the axillary region, are known in the prior art.Said body care agents are formulated in a wide range of product forms,for example as a powder, stick, aerosol spray, pump spray, liquid andgel roll-on application, cream, gel, and impregnated flexible substrates(deodorant wipes).

Cosmetic antiperspirants of the prior art include, in addition to atleast one oil or wax and one odorous substance component or perfume, atleast one antiperspirant compound, particularly in the form of halidesand/or hydroxy halides of aluminum and/or zirconium. Said antiperspirantcompounds reduce the secretion of sweat of the body by temporarilyconstricting and/or plugging the excretory ducts of the sweat glands sothat the amount of sweat can be reduced by approximately 20 to 60percent. Furthermore, said antiperspirant compounds have an additionaldeodorizing effect because of the antimicrobial action of saidantiperspirant compounds.

Halides and/or hydroxy halides of aluminum and/or zirconium, inconjunction with the acidic pH value of these antiperspirants, can leadto unpleasant skin reactions for some users. Furthermore, the use of theaforementioned antiperspirant compounds can lead to stains on clothing.

Therefore, there is a need for replacing antiperspirant halides and/orhydroxy halides of aluminum and/or zirconium with other antiperspirantcosmetic active substances. Said antiperspirant active substances shouldhave good antiperspirant action and good skin compatibility and shouldbe easy to formulate. Furthermore, said antiperspirant active substancesshould not have a negative effect on the storage stability of theantiperspirant cosmetic agents.

The present invention addresses the problem of providing anantiperspirant cosmetic agent that avoids or at least lessens thedisadvantages of the prior art and that has good skin compatibility andalso reliably reduces axillary moisture. Furthermore, the antiperspirantcosmetic agent should have high storage stability.

BRIEF SUMMARY OF THE INVENTION

Therefore, the subject of the present invention is an antiperspirantcosmetic agent, including

-   a) at least one substance selected from the group of cosmetic oils    that are liquid at 20° C. and 1,013 hPa, odorous substances, and    waxes,-   b) propellant in a total amount of 0 to 99 wt %, with respect to the    total weight of the antiperspirant cosmetic agent, and-   c) at least one chitosan having a viscosity of 15 to 15,000 mPa*s,    wherein the chitosan has the formula (I),

whereinx and z, independently of each other, represent integers from 5 to25,000,y represents integers from 1 to 25,000,R represents an NH₂ group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃⁺OHCH₂C(O)O⁻,with the stipulation that the sequence of the units contained in thesquare brackets and having the indices x, y, and z can be freely chosenand the residue R is bonded by means of *, and

-   d) no aluminum-containing compounds.

DETAILED DESCRIPTION OF THE INVENTION

The following detailed description of the invention is merely exemplaryin nature and is not intended to limit the invention or the applicationand uses of the invention. Furthermore, there is no intention to bebound by any theory presented in the preceding background of theinvention or the following detailed description of the invention.

It has now surprisingly been found that the use of at least one specificchitosan in cosmetic agents without aluminum-containing compounds,particularly without antiperspirant halides and/or hydroxy halides ofaluminum and/or zirconium, results in antiperspirant action that isnearly comparable to the antiperspirant action of formulations havingaluminum salts and/or aluminum-zirconium complexes.

With no intention of being restricted to this theory, the use of the atleast one chitosan in the antiperspirant cosmetic agents according tothe invention results in a deliberate influence on the sweat gland(s).Said deliberate influence on the sweat gland(s) can consist, forexample, in precipitation of the at least one chitosan at pH values thatexist only within the excretory ducts of the sweat glands. In this way,effective plugging of the excretory ducts of the sweat glands can beensured without a reduction in the antiperspirant action of the cosmeticagent according to the invention because of premature undesiredprecipitation due to the addition of the at least one specific protein.However, the deliberate influence on the sweat gland(s) can also consistin a disturbance of the charge equilibrium within the sweat gland(s),which leads to an effect on the production of sweat, particularly to areduction in the production of sweat. Therefore, an effective reductionin underarm perspiration is ensured even in the absence ofaluminum-containing compounds, particularly antiperspirant halidesand/or hydroxy halides of aluminum and/or zirconium.

According to the invention, the term “antiperspirant” is understood tomean the reduction of the perspiration of the sweat glands of the body.

Furthermore, in the sense of the present invention, the term “cosmeticoil” is understood to mean an oil that is suitable for cosmetic use andthat is not miscible with water in all amounts. The cosmetic oil usedaccording to the invention is neither an odorous substance nor anessential oil.

In addition, in the sense of the present invention, the term “odoroussubstances” is understood to mean substances that have a molar mass of74 to 300 g/mol, that include at least one osmophore in the molecule,and that have an odor and/or flavor, i.e., said substances are capableof stimulating the receptors of the hair cells of the olfactory system.Osmophores are groups, in the form of hydroxy groups, formyl groups, oxogroups, alkoxycarbonyl groups, nitrile groups, nitro groups, azidegroups, etc., that are covalently bonded to the molecular skeleton. Inthis context, perfume oils, perfumes, or perfume oil constituents thatare liquid at 20° C. and 1,013 hPa also fall under the term “odoroussubstances” in the sense of the present invention.

Furthermore, in the context of the present invention, the term “waxes”is understood to mean substances that are kneadable or solid to brittleand hard at 20° C., have a coarse to finely crystalline structure, andare colorfully translucent to opaque, but not vitreous. Furthermore,said substances melt above 25° C. without decomposition, flow readily(have low viscosity) slightly above the melting point, have a highlytemperature-dependent consistency and solubility, and can be polishedunder light pressure.

Furthermore, according to the invention, the term “chitosans” isunderstood to mean deacetylation products of chitin that have a degreeof deacetylation of more than 40% and that are soluble in 1% aqueoussolutions of suitable acids, such as acetic acid, formic acid, citricacid, lactic acid, or hydrochloric acid. The viscosity of the chitosansused according to the invention is determined by means of a BrookfieldRVDV II+, spindle no. 2, at 20 rpm and at 20° C., by using a 1 wt %solution of chitosan, with respect to the total weight of the solution,in 1% acetic acid.

Furthermore, in the context of the present invention, the term“aluminum-containing compounds” is understood to mean, in particular,chlorides, bromides, and iodides of aluminum and zirconium and compoundsof the formulas Al(OH)_(y)X and Zr(OH)_(z)X, wherein X represents ahalide ion in the aforementioned formulas.

In addition, the term “fatty acids,” as it is used in the context of thepresent invention, should be understood to mean aliphatic carboxylicacids that have unbranched or branched carbon residues having 4 to 40carbon atoms. The fatty acids used in the context of the presentinvention can be naturally occurring fatty acids or syntheticallyproduced fatty acids. Furthermore, the fatty acids can be mono- orpolyunsaturated.

Finally, in the context of the present invention, the term “fattyalcohols” should be understood to mean aliphatic, monohydric, primaryalcohols that have unbranched or branched hydrocarbon residues having 4to 40 carbon atoms. The fatty alcohols used in the context of theinvention can also be mono- or polyunsaturated.

In this document, the specification of wt % relates to the total weightof the propellant-free antiperspirant cosmetic agents according to theinvention, unless otherwise indicated.

As a first constituent a), the cosmetic agents according to theinvention include at least one substance selected from the group ofcosmetic oils that are liquid at 20° C. and 1,013 hPa, odoroussubstances, and waxes.

In the context of the present invention, the cosmetic oil that is liquidat 20° C. and 1,013 hPa is selected from the group of (i) volatilecyclic silicone oils, particularly cyclic and linear silicone oils; (ii)volatile non-silicone oils, particularly liquid paraffin oils andisoparaffin oils; (iii) non-volatile silicone oils; (iv) non-volatilenon-silicone oils; and (v) mixtures thereof

According to the invention, the term “volatile oil” refers to oils thathave a vapor pressure of 2.66 Pa to 40,000 Pa (0.02 to 300 mm Hg),preferably 10 to 12,000 Pa (0.1 to 90 mm Hg), more preferably 13 to3,000 Pa (0.1 to 23 mm Hg), particularly 15 to 500 Pa (0.1 to 4 mm Hg),at 20° C. and an ambient pressure 1,013 hPa.

Furthermore, in the sense of the present invention, the term“non-volatile oils” is understood to mean oils that have a vaporpressure of less than 2.66 Pa (0.02 mm Hg) at 20° C. and an ambientpressure of 1,013 hPa.

According to the invention, it can be preferred that mixtures ofvolatile silicone oils and volatile non-silicone oils are used in theantiperspirant cosmetic agents according to the invention, because adrier skin feel is thereby achieved. Furthermore, it can be preferred inthe context of the present invention if the antiperspirant cosmeticagents include a non-volatile silicone oil and/or a non-volatilenon-silicone oil in order to mask insoluble constituents, such as talcor ingredients that are dried on the skin.

Especially preferred according to the invention is the use of mixturesof non-volatile and volatile cosmetic oils, because in this wayparameters such as skin feel, visibility of the residue, and stabilityof the antiperspirant cosmetic agent according to the invention can beset and the agent can thus be better adapted to the needs of theconsumers.

The volatile and non-volatile silicone oils and volatile andnon-volatile non-silicone oils that can be used in the context of thepresent invention are disclosed, for example, in laid-open applicationsDE 102010063250 A1 and DE 10201222692 A1.

According to a preferred embodiment of the present invention, thecosmetic oil that is liquid at 20° C. and 1,013 hPa is included in atotal amount of 0.02 to 98 wt %, preferably 2 to 85 wt %, morepreferably 4 to 75 wt %, even more preferably 6 to 70 wt %, even morepreferably 8 to 60 wt %, particularly 8 to 20 wt %, with respect to thetotal weight of the propellant-free antiperspirant cosmetic agent.

At least one odorous substance can also be included as constituent a) ofthe cosmetic agents according to the invention. However, mixtures ofdifferent odorous substances that together produce a pleasant scent arepreferably used. Odorous substances that are usable in the context ofthe present invention are disclosed, for example, in laid-openapplication DE 102010063250 A1.

Especially pleasant-smelling antiperspirant cosmetic agents according tothe invention are obtained if the at least one odorous substance isincluded in a total amount of 0.00001 to 15 wt %, preferably 0.001 to 9wt %, more preferably 0.01 to 8 wt %, even more preferably 0.1 to 7 wt%, even more preferably 0.2 to 6 wt %, particularly 0.2 to 2 wt %, withrespect to the total weight of the propellant-free antiperspirantcosmetic agent.

Furthermore, the antiperspirant cosmetic agents according to theinvention can include a wax as constituent a). Said wax is preferablyselected from the group of (i) fatty acid glycerol mono-, di-, andtriesters; (ii) Butyrospermum Parkii (Shea Butter); (iii) esters ofsaturated, monohydric C₈₋₁₈ alcohols with saturated C₁₂₋₁₈monocarboxylic acids; (iv) linear, primary C₁₂₋₂₄ alkanols; (v) estersof a saturated, monohydric C₁₆₋₆₀ alkanol and a saturated C₈₋₃₆monocarboxylic acid; (vi) glycerol triesters of saturated linear C₁₂₋₃₀carboxylic acids, which can be hydroxylated; (vii) natural plant waxes;(viii) animal waxes; (ix) synthetic waxes; and (x) mixtures thereof.Waxes that can be used with preference in the context of the presentinvention are disclosed in laid-open application DE 102012222692 A1.

In the context of the present invention, it is preferred if the wax isincluded in a total amount of 0.01 to 50 wt %, preferably 3 to 40 wt %,more preferably 5 to 30 wt %, particularly 6 to 25 wt %, with respect tothe total weight of the propellant-free antiperspirant cosmetic agent.

According to one embodiment of the present invention, it can be providedthat the antiperspirant cosmetic agents according to the inventioninclude a propellant in a total amount of 0 to 99 wt %, with respect tothe total weight of the propellant-free antiperspirant cosmetic agent,as constituent b). If the cosmetic agents according to the inventioninclude a propellant, said propellant is preferably included in a totalamount of 1 to 98 wt %, preferably 20 to 90 wt %, more preferably 30 to85 wt %, particularly 40 to 75 wt %, with respect to the total weight ofthe antiperspirant cosmetic agent. In this case, the cosmetic agentsaccording to the invention are formulated as propellant-gas-drivenaerosols. Preferred propellants (propellant gases) are propane, propene,n-butane, isobutane, isobutylene, n-pentane, pentene, isopentane,isopentene, methane, ethane, dimethyl ether, nitrogen, air, oxygen,nitrous oxide, 1,1,1,3-tetrafluoroethane, heptafluoro-n-propane,perfluoroethane, monochlorodifluoromethane, 1,1-difluoroethane, andtetrafluoropropene, individually and in mixtures thereof. Hydrophilicpropellant gases, such as carbon dioxide, can also be advantageouslyused according to the present invention if the proportion of hydrophilicgases is low and lipophilic propellant gas (e.g., propane/butane) ispresent in excess. Propane, n-butane, isobutane, and mixtures of thesepropellant gases are especially preferred. It has been found that theuse of n-butane as a sole propellant gas can be especially preferredaccording to the invention.

The antiperspirant cosmetic agent according to the invention includes atleast one specific chitosan according to formula (I) as a thirdconstituent c).

Cosmetic agents according to the invention include at least one chitosanof formula (I) that has a viscosity of 15 to 15,000 mPa*s. Thepreviously stated viscosity is preferably determined by means of aBrookfield RVDV II+, spindle no. 2, at 20 rpm and at 20° C., by using 1wt % of chitosan of formula (I) in a 1 wt % acetic acid solution, withrespect to the total weight of the solution. The solution is understoodto be a 1 wt % acetic acid solution in which 1 wt % of the chitosan and1 wt % of acetic acid, with respect to the total weight of saidsolution, are dissolved.

According to a preferred embodiment of the present invention, yrepresents integers from 1 to 22,000, preferably from 1 to 20,000, morepreferably from 1 to 19,000, even more preferably from 1 to 18,000,particularly from 1 to 17,500, in formula (I).

Furthermore, it is preferred in the context of the present invention ifx and z, independently of each other, represent integers from 5 to20,000, preferably from 6 to 15,200, more preferably from 7 to 13,000,even more preferably from 8 to 12,500, particularly from 10 to 11,700,in formula (I). The use of chitosans of formula (I) having thepreviously stated numerical values for x, y, and z leads to anespecially effective influence on the sweat gland(s) and therefore to anespecially large reduction in perspiration.

In the context of the present invention, especially good results areobtained if chitosans of formula (I) that have a certain degree ofdeacetylation are used. Therefore, preferred antiperspirant cosmeticagents according to the invention are characterized in that the at leastone chitosan of formula (I) has a degree of deacetylation of 70 to 99%,preferably 80 to 98%, more preferably 80 to 95%, even more preferably 80to 92%, particularly 80 to 90%. The degree of deacetylation can bedetermined, for example, by means of NMR spectroscopy (Hwang, K. T. etal.; J. Agric. Food Chem.; 2002, 50, pages 1876 to 1882). Chitosans thathave a degree of deacetylation of less than 70% have only insufficientsolubility and therefore are not suitable for use in the antiperspirantagents according to the invention, because, as a result of theinsolubility, the chitosan cannot enter the excretory ducts of the sweatgland(s) and therefore perspiration cannot be reduced.

The chitosan of formula (I) used in the antiperspirant cosmetic agentsaccording to the invention can be obtained from various sources.However, it is preferred if the at least one chitosan of formula (I) isisolated from marine sources, particularly crabs, shrimps, krill, fungi,zooplankton, insects, microorganisms, modified microorganisms, or plantsources. The chitosan of formula (I) used in the antiperspirant cosmeticagents according to the invention is preferably obtained from marinesources, particularly from the chitin of crustaceans, which arise inlarge amounts in the preparation of crabs, lobsters, shrimps, etc. forfood purposes. The chitin included there is typically deprotonated bythe addition of bases, demineralized by the addition of mineral acids,and then deacetylated by using strong bases, such as concentrated sodiumhydroxide solution. However, besides this production method, thechitosan of formula (I) can also be obtained from lower fungi such asAbsidia sp., Rhizopus sp., and Mucor sp., which have chitosan as a cellwall component. Furthermore, it is also possible to obtain chitosan offormula (I) by using genetically modified microorganisms that synthesizechitosan by means of enzymatic processes. Chitosan can also be obtainedfrom chitosan-containing plant sources.

In the context of the present invention, it is advantageous if thechitosans of formula (I) have a certain molecular weight. Therefore,preferred antiperspirant cosmetic agents according to the invention arecharacterized in that the at least one chitosan of formula (I) has anaverage molecular weight M_(w) of 5,000 to 6,000,000 Da, preferably6,000 to 5,500,000 Da, more preferably 8,000 to 5,050,000 Da,particularly 10,000 to 5,000,000 Da. The average molecular weight M_(w)can be determined, for example, by gel permeation chromatography (GPC)(Hwang, K. T. et al.; J. Agric. Food Chem.; 2002, 50, pages 1876 to1882). The use of chitosans having the previously stated molecularweights leads to an especially effective influence on the sweat gland(s)by precipitation of the chitosan within the sweat gland(s) or bydisturbance of the charge equilibrium within the sweat gland(s) andtherefore to excellent antiperspirant action of the cosmetic agentsaccording to the invention.

According to the invention, chitosans of formula (I) that have a certainviscosity are especially preferably used. Therefore, it is preferred inthe context of the present invention if the at least one chitosan offormula (I) has a viscosity of 15 to 10,000 mPa*s, preferably 15 to8,000 mPa*s, more preferably 15 to 6,000 mPa*s, particularly 15 to 5,000mPa*s, wherein the viscosity is determined by means of a Brookfield RVDVII+, spindle no. 2, at 20 rpm and at 20° C., and wherein 1 wt % ofchitosan of formula (I) in a 1 wt % acetic acid solution, with respectto the total weight of the solution, is used to determine the viscosity.Chitosans that have a viscosity below 15 mPa*s do not result in thedesired influence on the sweat gland(s). In contrast, chitosans having aviscosity of more than 15,000 mPa*s lead to formulation problems andusage problems of the cosmetic agents according to the invention becauseof the high viscosity and therefore are also not suitable in the contextof the present invention.

In the context of the present invention, an especially effectivereduction in underarm perspiration by means of the at least one chitosanof formula (I) is achieved if the at least one chitosan of formula (I)is included in a total amount of 0.05 to 40 wt %, preferably 0.1 to 35wt %, more preferably 0.2 to 30 wt %, even more preferably 0.4 to 25 wt%, particularly 0.5 to 20 wt %, with respect to the total weight of thepropellant-free antiperspirant cosmetic agent. With no intention ofbeing restricted to this theory, the use of the aforementioned amountsof the at least one specific chitosan results in a significant influenceon the sweat gland(s) by precipitation of the chitosan in the excretoryducts of the sweat glands or by an effect on the charge equilibriumwithin the sweat gland(s). In this way, excellent antiperspirant actionis ensured. Furthermore, the use of the aforementioned amounts of the atleast one specific chitosan does not lead to unstable formulations, andtherefore the stability of the antiperspirant cosmetic agents accordingto the invention is ensured even over long time periods of storage.

According to another preferred embodiment of the present invention, theantiperspirant cosmetic agent has a pH value of pH 2 to pH 10. Withinthis range, a stable formulation of the cosmetic agents according to theinvention is possible without the occurrence of undesired interactionsbetween the ingredients. According to the invention, the desired pHvalue can be set by using acids and bases that are known to a personskilled in the art and that are common in antiperspirant cosmeticagents.

According to the invention, it is also preferred if the antiperspirantcosmetic agent additionally includes at least one preservative agent.Preservative agents preferred according to the invention areiodopropynyl butylcarbamate formaldehyde releaser, parabens,phenoxyethanol, ethanol, benzoic acid and salts thereof,dibromodicyanobutane, 2-bromo-2-nitropropane-1,3-diol, imidazolidinylurea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide,benzalkonium chloride, benzyl alcohol, salicylic acid, and salicylates.Other preservative agents that are usable in the context of the presentinvention are the substances listed in Annex 6 of the CosmeticsRegulation and cosmetic raw materials having preservative properties orraw materials that support or intensify the preservative action of theaforementioned preservative agents. The preservative agents arepreferably included in a total amount of 0.01 to 10 wt %, preferably 0.1to 7 wt %, more preferably 0.2 to 5 wt %, particularly 0.3 to 2.0 wt %,with respect to the total weight of the propellant-free antiperspirantcosmetic agent.

In the context of the present invention, it is preferred if theantiperspirant cosmetic agent exists in the form of a water-in-oilemulsion. In particular, the water-in-oil emulsion can be a sprayablewater-in-oil emulsion, which can be sprayed by means of a propellant, ora gel-type water-in-oil emulsion, which can be applied by means of adispenser. In this context, it is preferred if the antiperspirantcosmetic agent according to the invention existing in the form of awater-in-oil emulsion includes the at least one chitosan of formula (I)in a total amount of 0.05 to 40 wt %, preferably 0.1 to 35 wt %, morepreferably 0.2 to 30 wt %, even more preferably 0.4 to 25 wt %,particularly 0.5 to 20 wt %, with respect to the total weight of thepropellant-free antiperspirant cosmetic agent.

However, it can be equally preferred according to the invention if theantiperspirant cosmetic agent exists as an oil-in-water emulsion. Inthis case, the cosmetic agent according to the invention is preferablysprayed as a propellant-containing aerosol or a propellant-free pumpspray or squeeze spray or applied as a roll-on. In this context, it ispreferred if the antiperspirant cosmetic agent existing in the form ofan oil-in-water emulsion includes the at least one chitosan of formula(I) in a total amount of 0.05 to 40 wt %, preferably 0.1 to 35 wt %,more preferably 0.2 to 30 wt %, even more preferably 0.4 to 25 wt %,particularly 0.5 to 20 wt %.

According to another preferred embodiment of the present invention, thecosmetic agents according to the invention can include only a smallcontent of free water or no free water. In the sense of the presentinvention, the term “free water” is understood to mean water that isdifferent from water of crystallization, hydration water, or similarlymolecularly bound water of the constituents that are used. Theantiperspirant cosmetic agent preferably includes free water in a totalamount of less than 10 wt %, preferably less than 8 wt %, morepreferably less than 5 wt %, even more preferably less than 3 wt %, evenmore preferably less than 1 wt %, particularly 0 wt %, with respect tothe total weight of the propellant-free antiperspirant cosmetic agent.

However, in the context of another embodiment, it is also preferredaccording to the invention if the antiperspirant cosmetic agent existsas an aqueous, aqueous-alcoholic, or aqueous-glycolic solution.According to the invention, because the cosmetic agents according to theinvention include no antiperspirant halides and/or hydroxy halides ofaluminum and/or zirconium, which have reduced antiperspirant action as aresult of the addition of protic solvents, protic solvents such asaqueous solutions can be used to formulate the antiperspirant cosmeticagents according to the invention without the occurrence of asignificant reduction in the antiperspirant action. Therefore, theaddition of the at least one specific chitosan ensures an effectiveinfluence on the sweat gland(s) and thus excellent antiperspirant actioneven if protic solvents are used.

In the context of this embodiment of the present invention, it wassurprisingly found that the influence on the sweat gland(s) by the atleast one specific chitosan of formula (I) can be significantlyincreased if the antiperspirant cosmetic agents according to theinvention include free water in an amount of 5 to 99 wt %, with respectto the total weight of the propellant-free antiperspirant cosmeticagent. Therefore, in an especially preferred embodiment of the presentinvention, the antiperspirant cosmetic agent includes free water in atotal amount of 5 to 96 wt %, preferably 15 to 80 wt %, more preferably30 to 70 wt %, particularly 40 to 60 wt %, with respect to the totalweight of the propellant-free antiperspirant cosmetic agent.

Furthermore, in the context of this embodiment, it is preferred if theantiperspirant cosmetic agent includes ethanol in a total amount of 1 to99 wt %, preferably 5 to 70 wt %, more preferably 7 to 50 wt %,particularly 10 to 30 wt %, with respect to the total weight of thepropellant-free antiperspirant cosmetic agent. As previously stated,because of the use of the at least one specific chitosan of formula (I),even large amounts of protic solvents such as ethanol can be usedwithout the antiperspirant action of the antiperspirant cosmetic agentaccording to the invention being negatively affected.

The antiperspirant cosmetic agent according to the invention can beapplied by means of various methods. According to a preferredembodiment, the antiperspirant cosmetic agent is formulated as a sprayapplication. The spray application is accomplished by means of aspraying device, which includes a filling of the antiperspirant cosmeticagent according to the invention, which is liquid, viscously flowable,in the form of a suspension, or in the form of a powder, in a container.The filling can be under the pressure of a propellant (compressed-gascans, compressed-gas packages, aerosol packages), or a mechanicallyoperated pump atomizer without propellant gas (pump sprays/squeezebottle) can be used. The antiperspirant cosmetic agent can be atomizedphysically, mechanically, or electromechanically, for example by meansof piezoelectric effects or electric pumps. Containers and removaldevices that are usable in the context of this embodiment are described,for example, in laid-open application DE 102012222692 A1.

Furthermore, the antiperspirant cosmetic agent can preferably beformulated as a stick, soft solid, cream, gel, roll-on, or loose orcompact powder. The formulation of the antiperspirant cosmetic agentsaccording to the invention in a certain product form, such as anantiperspirant roll-on, an antiperspirant stick, or an antiperspirantgel, is preferably based on the requirements of the intended use.Therefore, depending on the intended use, the antiperspirant cosmeticagents according to the invention can exist in solid, semisolid, liquid,disperse, emulsified, suspended, gel, multi-phase, or powdery form. Inthe sense of the present invention, all types of solid dispersions inliquids also fall under the term “liquid”. Furthermore, in the sense ofthe present invention, agents that have at least two different phaseshaving a phase separation and in the case of which the phases can bearranged horizontal, i.e., one over the other, or vertical, i.e., onenext to the other, are understood by multi-phase antiperspirant cosmeticagents according to the invention. The application can be performed, forexample, by means of a roller-ball applicator or by means of a solidstick.

In the context of the present invention, it can also be preferred if theantiperspirant cosmetic agent is included on and/or in a disposablesubstrate, selected from the group of wipes, pads, and puffs. Especiallypreferred are wet wipes, i.e., preferably individually packaged wetwipes prefabricated for the user, which are well known, for example,from the field of glass cleaning or from the field of wet toilet wipes.Such wet wipes, which can advantageously also include preservativesubstances, are impregnated or loaded with an antiperspirant cosmeticagent according to the invention and are preferably packagedindividually. Preferred substrate materials are selected from porousflat wipes. These wipes include wipes composed of woven and nonwovensynthetic and natural fibers, felt, paper, or foam, such as hydrophilicpolyurethane foam. Deodorizing or antiperspirant substrates preferredaccording to the invention can be obtained by soaking or impregnation orby applying an antiperspirant cosmetic agent according to the inventionto a substrate in melted form.

Besides the previously mentioned compounds, the antiperspirant cosmeticagent according to the invention can include further active substancesand ingredients.

According to the invention, it is therefore preferred that theantiperspirant cosmetic agent includes at least one further auxiliarysubstance, selected from the group of (i) emulsifiers and/orsurfactants; (ii) thickeners; (iii) chelating agents; (iv) deodorantactive substances; (v) mono- and/or polyhydric alcohols and/orpolyethylene glycols; (vi) skin-cooling active substances; (vii) pHadjusters; (viii) skin care active substances, such as moisturizers,skin-soothing substances, skin-lightening substances, skin-smoothingsubstances; and (ix) mixtures thereof.

Suitable emulsifiers and surfactants preferred according to theinvention are selected from anionic, cationic, non-ionic, amphoteric,particularly ampholytic and zwitterionic emulsifiers and surfactants.Surfactants are amphiphilic (bifunctional) compounds that consist of atleast one hydrophobic molecule part and at least one hydrophilicmolecule part. The hydrophobic residue is preferably a hydrocarbon chainhaving 8 to 28 carbon atoms, which hydrocarbon chain can be saturated orunsaturated, linear or branched. This C₈-C₂₈ alkyl chain is especiallypreferably linear. Emulsifiers and surfactants that are usable withpreference in the context of the present invention are disclosed, forexample, in laid-open applications DE 102012222692 A1, DE 102010063250A1, and DE 102010055816 A1.

To thicken the antiperspirant cosmetic agents according to theinvention, preferably substances selected from the following are used:cellulose ethers, xanthan gum, sclerotium gum, succinoglucans,polygalactomannans, pectins, agar, carrageenan, tragacanth, gum arabic,gum karaya, tara gum, gellan gum, gelatin, propylene glycol alginate,alginic acids and salts thereof, polyvinylpyrrolidones, polyvinylalcohols, polyacrylamides, starches that are physically modified (e.g.,by means of pre-gelatinization) and/or chemically modified, acrylicacid/acrylate copolymers, acrylic acid/acrylamide copolymers, acrylicacid/vinylpyrrolidone copolymers, acrylic acid/vinylformamidecopolymers, and polyacrylates. Furthermore, especially preferredthickeners are selected from carbomers. Carbomers are thickeningcross-linked polymers of acrylic acid, methacrylic acid, and saltsthereof. The cross-linking can be accomplished by means ofpolyfunctional compounds such as polyalkylene ethers of polysaccharidesor of polyalcohols, such as sucrose allyl ethers, pentaerythritol allylethers, propylene allyl ethers. Homopolymers of acrylic acid or saltsthereof that are cross-linked by means of a pentaerythritol allyl ether,a sucrose allyl ether, or a propylene allyl ether are preferred in thecontext of the present invention. A copolymer of C₁₀₋₃₀ alkyl acrylate,acrylic acid, methacrylic acid, and esters thereof that is cross-linkedby means of a sucrose allyl ether or a pentaerythritol allyl ether is athickener that is usable in the context of the present invention. Theproducts available under the trade name Carbopol® (BF Goodrich, Ohio,USA), such as Carbopol 934, Carbopol 940, Carbopol 941, Carbopol 971,Carbopol 974, Carbopol EZ2, Carbopol ETD 2001, Carbopol ETD 2020,Carbopol ETD 2050, Carbopol ultrez 10, Carbopol ultrez 20, or Carbopolultrez 21, are thickeners based on carbomers.

Furthermore, lipophilic thickeners can be used to thicken theantiperspirant cosmetic agents according to the invention. Lipophilicthickeners preferred according to the invention are selected fromhydrophobed clay minerals, bentonites, pyrogenic silicic acids, andderivatives thereof

To further support the influence of the at least one specific chitosanof formula (I) on the sweat gland(s), it can be advantageous to add atleast one chelating agent to the antiperspirant cosmetic agentsaccording to the invention in a total amount of 0.01 to 3.0 wt %,preferably 0.02 to 1.0 wt %, particularly 0.05 to 0.1 wt %, with respectto the total weight of the propellant-free antiperspirant agentaccording to the invention. In the context of the present invention,preferred chelating agents are selected from the group of β-alaninediacetic acid, cyclodextrin, diethylenetriamine penta(methylenephosphonic acid), sodium, potassium, calcium disodium, ammonium, andtriethanolamine salts of ethylenediamine tetraacetic acid (EDTA),etidronic acid, hydroxyethyl ethylenediamine tetraacetic acid (HEDTA)and sodium salts thereof, sodium salts of nitrilotriacetic acid (NTA),diethylenetriamine pentaacetic acid, phytic acid, hydroxypropylcyclodextrin, methyl cyclodextrin, pentasodium amino trimethylenephosphonate, pentasodium ethylenediamine tetramethylene phosphonate,pentasodium diethylenetriaminepentaacetate, pentasodium triphosphate,potassium EDTMP, sodium EDTMP, sodium dihydroxyethylglycinate, sodiumphytate, sodium polydimethylglycinophenol sulfonate, tetrahydroxyethylethylenediamine, tetrahydroxypropyl ethylenediamine, tetrapotassiumetidronate, tetrasodium etidronate, tetrasodium iminodisuccinate,trisodium ethylenediamine disuccinate, tetrasodiumN,N-bis(carboxymethyl)-glutamate, tetrasodium DL-alanine-N,N-diacetate,and desferrioxamine.

The deodorizing action of the antiperspirant cosmetic agents accordingto the invention can be increased further if at least one deodorantactive substance having antibacterial and/or bacteriostatic and/orenzyme-inhibiting and/or odor-neutralizing and/or odor-absorbing actionis additionally included in a total amount of 0.0001 to 40 wt %,preferably 0.2 to 20 wt %, more preferably 1 to 15 wt %, particularly1.5 to 5 wt %, with respect to the total weight of the propellant-freeantiperspirant cosmetic agent according to the invention. If ethanol isused in the agents according to the invention, the ethanol is notconsidered to be a deodorant active substance in the context of thepresent invention, but rather a constituent of the carrier. Deodorantactive substances preferred according to the invention are disclosed,for example, in laid-open application DE 102010063250 A1.

Preferred antiperspirant cosmetic agents according to the invention alsoinclude at least one water-soluble polyhydric C₂₋₉ alkanol having 2 to 6hydroxyl groups and/or at least one water-soluble polyethylene glycolhaving 3 to 50 ethylene oxide units and mixtures thereof. Theaforementioned deodorant active substances in the form of1,2-alkanediols do not fall thereunder. Preferred alkanols andwater-soluble polyethylene glycols are described, for example, inlaid-open application DE 102010063250 A1.

According to another embodiment of the present invention, theantiperspirant cosmetic agents also include at least one skin-coolingactive substance. Skin-cooling active substances suitable according tothe invention are, for example, menthol, isopulegol, and mentholderivatives, e.g., menthyl lactate, menthyl glycolate, menthyl ethyloxamate, menthyl pyrrolidone carboxylic acid, menthyl methyl ether,menthoxypropanediol, menthone glycerin acetal(9-methyl-6-(1-methylethyl)-1,4-dioxaspiro[4.5]decane-2-methanol),monomenthyl succinate, 2-hydroxymethyl-3,5,5-trimethylcyclohexanol, and5-methyl-2-(1-methylethyl)cyclohexyl-N-ethyloxamate. Menthol,isopulegol, menthyl lactate, menthoxypropanediol, menthyl pyrrolidonecarboxylic acid, and 5-methyl-2-(1-methylethyl)cyclohexyl-N-ethyloxamateand mixtures of these substances, particularly mixtures of menthol andmenthyl lactate, menthol, menthol glycolate, and menthyl lactate,menthol and menthoxypropanediol, or menthol and isopulegol, arepreferred as skin-cooling active substances.

According to the invention, preferably acids and/or alkalizing agentsand/or buffers are used as pH adjusters. According to the invention,preferably inorganic acids (such as hydrochloric acid, sulfuric acid, orphosphoric acid) or organic acids (such as citric acid, gluconic acid,tartaric acid, or malic acid) are used as acids. The alkalizing agentsthat are usable according to the invention are preferably selected fromthe group consisting of ammonia, basic amino acids, alkali hydroxides,carbonates and hydrogencarbonates, alkanolamines, such asamino-2-methyl-1-propanol, monoethanolamine, triethanolamine,diethanolamine, and triisopropanolamine, alkali metal metasilicates,urea, morpholine, N-methylglucamine, imidazole, alkali phosphates, andalkali hydrogenphosphates. Preferably lithium, sodium, potassium,particularly sodium or potassium, is used as an alkali metal ion. Inparticular, carbonic acid/bicarbonate buffer, carbonic acid/silicatebuffer, acetic acid/acetate buffer, phosphate buffer, ammonia buffer,citric acid or citrate buffer, buffer based ontris(hydroxymethyl)aminomethane, buffer based on4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, buffer based on4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid, buffer based on2-(N-morpholino)ethanesulfonic acid, and barbital/acetate buffer aresuitable as buffer systems in the context of the present invention. Theappropriate buffer system is selected in accordance with the desired pHvalue of the antiperspirant cosmetic agents according to the invention.

In a preferred embodiment, the antiperspirant cosmetic agents accordingto the invention are characterized in that said agents include—withrespect to the total weight of the propellant-free antiperspirantcosmetic agent—

-   -   at least one chitosan of formula (I) in a total amount of 0.05        to 40 wt %, preferably 0.1 to 35 wt %, more preferably 0.2 to 30        wt %, even more preferably 0.4 to 25 wt %, particularly 0.5 to        20 wt %,    -   12 to 98 wt %, preferably 25 to 55 wt %, more preferably 30 to        50 wt %, particularly 35 to 45 wt %, of water,    -   at least one emulsifier and/or one surfactant,    -   at least one pH adjuster,    -   at least one preservative agent, and    -   at least one substance selected from the group of cosmetic oils        that are liquid at 20° C. and 1,013 hPa, odorous substances, and        waxes.

In another preferred embodiment, the antiperspirant cosmetic agentsaccording to the invention are characterized in that said agentsinclude—with respect to the total weight of the propellant-freeantiperspirant cosmetic agent according to the invention—

-   -   at least one chitosan of formula (I) in a total amount of 0.05        to 40 wt %, preferably 0.1 to 35 wt %, more preferably 0.2 to 30        wt %, even more preferably 0.4 to 25 wt %, particularly 0.5 to        20 wt %,    -   12 to 98 wt %, preferably 25 to 55 wt %, more preferably 30 to        50 wt %, particularly 35 to 45 wt %, of water,    -   at least one emulsifier and/or one surfactant,    -   at least one pH adjuster,    -   at least one preservative agent,    -   0.01 to 5 wt %, preferably 0.1 to 2 wt %, more preferably 0.2 to        0.7 wt %, particularly 0.3 to 0.5 wt %, of a thickener, and    -   at least one substance selected from the group of cosmetic oils        that are liquid at 20° C. and 1,013 hPa, odorous substances, and        waxes.

In a preferred embodiment, the antiperspirant cosmetic agents accordingto the invention are characterized in that said agents include—withrespect to the total weight of the propellant-free antiperspirantcosmetic agent according to the invention—

-   -   at least one chitosan of formula (I) in a total amount of 0.05        to 40 wt %, preferably 0.1 to 35 wt %, more preferably 0.2 to 30        wt %, even more preferably 0.4 to 25 wt %, particularly 0.5 to        20 wt %,    -   12 to 98 wt %, preferably 25 to 55 wt %, more preferably 30 to        50 wt %, particularly 35 to 45 wt %, of water,    -   at least one propellant in a total amount of 1 to 98 wt %,        preferably 20 to 90 wt %, more preferably 30 to 85 wt %,        particularly 40 to 75 wt %,    -   at least one emulsifier and/or one surfactant,    -   at least one pH adjuster,    -   at least one preservative agent, and    -   at least one substance selected from the group of cosmetic oils        that are liquid at 20° C. and 1,013 hPa, odorous substances, and        waxes.

In another preferred embodiment, the antiperspirant cosmetic agentsaccording to the invention are characterized in that said agentsinclude—with respect to the total weight of the propellant-freeantiperspirant cosmetic agent according to the invention—

-   -   at least one chitosan of formula (I) in a total amount of 0.05        to 40 wt %, preferably 0.1 to 35 wt %, more preferably 0.2 to 30        wt %, even more preferably 0.4 to 25 wt %, particularly 0.5 to        20 wt %,    -   12 to 98 wt %, preferably 25 to 55 wt %, more preferably 30 to        50 wt %, particularly 35 to 45 wt %, of water,    -   at least one propellant in a total amount of 1 to 98 wt %,        preferably 20 to 90 wt %, more preferably 30 to 85 wt %,        particularly 40 to 75 wt %,    -   at least one emulsifier and/or one surfactant,    -   at least one pH adjuster,    -   at least one preservative agent,    -   0.01 to 5 wt %, preferably 0.1 to 2 wt %, more preferably 0.2 to        0.7 wt %, particularly 0.3 to 0.5 wt %, of a thickener, and    -   at least one substance selected from the group of cosmetic oils        that are liquid at 20° C. and 1,013 hPa, odorous substances, and        waxes.

In the context of the present invention, it can also be provided thatthe cosmetic agent according to the invention is formulated as atwo-component agent. For this purpose, the individual components arepreferably stored in separate containers and are applied to the skin oneafter the other in any order or simultaneously. Separation intomulti-component systems is preferred particularly if incompatibility ofthe ingredients is expected or feared.

Therefore, another subject of the present invention is a packaging unit(kit of parts), comprising—produced separate from each other—

-   a) at least one first container (C1), containing a cosmetic agent    (M1) comprising at least one antiperspirant active substance, and-   b) at least one second container (C2), containing a cosmetic agent    (M2) comprising at least one chitosan of formula (I),

whereinx and z, independently of each other, represent integers from 5 to25,000,y represents integers from 1 to 25,000,R represents an NH₂ group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃⁺OHCH₂C(O)O⁻,with the stipulation that the sequence of the units included in thesquare brackets and having the indices x, y, and z can be freely chosenand the residue R is bonded by means of *, and wherein the cosmeticagent (M2) includes no aluminum-containing compounds.

According to the invention, the term “antiperspirant active substance”is understood to mean active substances that reduce the perspiration ofthe sweat glands of the body. However, the chitosans of formula (I) thatare included in the cosmetic agent (M2) do not fall thereunder.

The statements made with respect to the cosmetic agents according to theinvention apply, mutatis mutandis, to other embodiments of the packagingunit according to the invention.

Another subject of the present invention is the use of at least onechitosan to at least partially influence the sweat gland(s), wherein thechitosan has the formula (I),

whereinx and z, independently of each other, represent integers from 5 to25,000,y represents integers from 1 to 25,000,R represents an NH₂ group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃⁺OHCH₂C(O)O⁻, with the stipulation that the sequence of the unitsincluded in the square brackets and having the indices x, y, and z canbe freely chosen and the residue R is bonded by means of *.

According to the invention, “to influence the sweat gland(s)” and“influence on the sweat gland(s)” should be understood to mean theinfluencing of the sweat gland(s) in such a way that the secretion ofsweat from the excretory duct is avoided or reduced. With no intentionof being restricted to one theory, this can be accomplished by theformation of a precipitate of the at least one specific chitosan offormula (I) in the excretory duct of the sweat gland or the excretoryducts of the sweat glands. However, this can also be accomplished bydisturbing the charge equilibrium within the excretory ducts of thesweat glands.

The statements made with respect to the antiperspirant cosmetic agentsaccording to the invention apply, mutatis mutandis, to other embodimentsof the use according to the invention.

Furthermore, another subject of the present invention is the use of acombination, including

-   a) at least one substance selected from the group of cosmetic oils    that are liquid at 20° C. and 1,013 hPa, odorous substances, and    waxes,-   b) propellant in a total amount of 0 to 99 wt %, with respect to the    total weight of the antiperspirant cosmetic agent, and-   c) at least one chitosan having a viscosity of 15 to 15,000 mPa*s,    wherein the chitosan has the formula (I),

whereinx and z, independently of each other, represent integers from 5 to25,000,y represents integers from 1 to 25,000,R represents an NH₂ group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃⁺OHCH₂C(O)O⁻,with the stipulation that the sequence of the units included in thesquare brackets and having the indices x, y, and z can be freely chosenand the residue R is bonded by means of *, and

-   d) no aluminum-containing compounds,    to reduce and/or prevent perspiration, particularly underarm    perspiration or perspiration of other body regions.

In the sense of the present invention, the term “combination” comprisesa mixture of the ingredients a), b), and c) that are specified above.The statements made with respect to the antiperspirant cosmetic agentsaccording to the invention and to the use according to the inventionapply, mutatis mutandis, to other preferred embodiments of the use ofthe aforementioned combination.

Finally, another subject of the present invention is a non-therapeuticcosmetic method for preventing and/or reducing the perspiration of thebody, wherein an antiperspirant cosmetic agent according to theinvention or the cosmetic agents (M1) and (M2) of the packaging unitaccording to the invention are applied to the skin, particularly to theskin of the axillae, and remain on the skin of the axillae for at least1 hour, preferably for at least 2 hours, more preferably for at least 4hours, particularly for at least 6 hours.

In the case of the packaging unit according to the invention, it can beprovided that first the cosmetic agent (M1) having the antiperspirantactive substance is applied and then the cosmetic agent (M2) includingat least one chitosan of formula (I) is applied. But it is also possiblethat first the cosmetic agent (M2) is applied and then a cosmetic agent(M1) is used. Furthermore, the cosmetic agent (M2) and the cosmeticagent (M1) can also be applied to the skin simultaneously. The time spanbetween the application of said two agents is 0 seconds to 24 hours.

Furthermore, in the context of this subject of the invention, it ispreferred if the cosmetic agent or the cosmetic agents remain on theskin of the axillae for at least 1 hour, preferably for at least 2hours, more preferably for at least 4 hours, particularly for at least 6hours, after the application.

The statements made with respect to the antiperspirant cosmetic agentsaccording to the invention and to the use according to the inventionapply, mutatis mutandis, to other preferred embodiments of the methodaccording to the invention.

The present invention is outlined particularly by means of the followingpoints:

An antiperspirant cosmetic agent, including

-   a) at least one substance selected from the group of cosmetic oils    that are liquid at 20° C. and 1,013 hPa, odorous substances, and    waxes,-   b) propellant in a total amount of 0 to 99 wt %, with respect to the    total weight of the antiperspirant cosmetic agent, and-   c) at least one chitosan having a viscosity of 15 to 15,000 mPa*s,    wherein the chitosan has the formula (I),

whereinx and z, independently of each other, represent integers from 5 to25,000,y represents integers from 1 to 25,000,R represents an NH₂ group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃⁺OHCH₂C(O)O⁻,with the stipulation that the sequence of the units included in thesquare brackets and having the indices x, y, and z can be freely chosenand the residue R is bonded by means of *, and

-   d) no aluminum-containing compounds.

The antiperspirant cosmetic agent according to point 1, characterized inthat the viscosity is determined by means of a Brookfield RVDV II+,spindle no. 2, at 20 rpm and at 20° C., by using 1 wt % of chitosan offormula (I) in a 1 wt % acetic acid solution, with respect to the totalweight of the solution.

The antiperspirant cosmetic agent according to one of points 1 and 2,characterized in that y represents integers from 1 to 22,000, preferablyfrom 1 to 20,000, more preferably from 1 to 19,000, even more preferablyfrom 1 to 18,000, particularly from 1 to 17,500, in formula (I).

The antiperspirant cosmetic agent according to one of the precedingpoints, characterized in that x and z, independently of each other,represent integers from 5 to 20,000, preferably from 6 to 15,200, morepreferably from 7 to 13,000, even more preferably from 8 to 12,500,particularly from 10 to 11,700, in formula (I).

The antiperspirant cosmetic agent according to one of the precedingpoints, characterized in that the at least one chitosan of formula (I)has a degree of deacetylation of 70 to 99%, preferably 80 to 98%, morepreferably 80 to 95%, even more preferably 80 to 92%, particularly 80 to90%.

The antiperspirant cosmetic agent according to one of the precedingpoints, characterized in that the at least one chitosan of formula (I)is isolated from marine sources, particularly crabs, shrimps, krill,fungi, zooplankton, insects, microorganisms, modified microorganisms, orplant sources.

The antiperspirant cosmetic agent according to one of the precedingpoints, characterized in that the at least one chitosan of formula (I)has an average molecular weight M_(w) of 5,000 to 6,000,000 Da,preferably 6,000 to 5,500,000 Da, more preferably 8,000 to 5,050,000 Da,particularly 10,000 to 5,000,000 Da.

The antiperspirant cosmetic agent according to one of the precedingpoints, characterized in that the at least one chitosan of formula (I)has a viscosity of 15 to 10,000 mPa*s, preferably 15 to 8,000 mPa*s,more preferably 15 to 6,000 mPa*s, particularly 15 to 5,000 mPa*s,wherein the viscosity is determined by means of a Brookfield RVDV II+,spindle no. 2, at 20 rpm and at 20° C., and wherein 1 wt % of chitosanof formula (I) in a 1 wt % acetic acid solution, with respect to thetotal weight of the solution, is used to determine the viscosity.

The antiperspirant cosmetic agent according to one of the precedingpoints, characterized in that the at least one chitosan of formula (I)is included in a total amount of 0.05 to 40 wt %, preferably 0.1 to 35wt %, more preferably 0.2 to 30 wt %, even more preferably 0.4 to 25 wt%, particularly 0.5 to 20 wt %, with respect to the total weight of thepropellant-free antiperspirant cosmetic agent.

The antiperspirant cosmetic agent according to one of the precedingclaims, characterized in that the antiperspirant cosmetic agent has a pHvalue of pH 2 to pH 6.

A packaging unit (kit of parts), comprising—produced separate from eachother—

-   a) at least one first container (C1), containing a cosmetic agent    (M1) comprising at least one antiperspirant active substance, and-   b) at least one second container (C2), containing a cosmetic agent    (M2) comprising at least one chitosan of formula (I),

whereinx and z, independently of each other, represent integers from 5 to25,000,y represents integers from 1 to 25,000,R represents an NH₂ group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃⁺OHCH₂C(O)O⁻,with the stipulation that the sequence of the units included in thesquare brackets and having the indices x, y, and z can be freely chosenand the residue R is bonded by means of *, andwherein the cosmetic agent (M2) includes no aluminum-containingcompounds.

The use of at least one chitosan to at least partially influence thesweat gland(s), wherein the chitosan has the formula (I),

whereinx and z, independently of each other, represent integers from 5 to25,000,y represents integers from 1 to 25,000,R represents an NH₂ group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃⁺OHCH₂C(O)O⁻,with the stipulation that the sequence of the units included in thesquare brackets and having the indices x, y, and z can be freely chosenand the residue R is bonded by means of *.

The use of a combination, including

-   a) at least one substance selected from the group of cosmetic oils    that are liquid at 20° C. and 1,013 hPa, odorous substances, and    waxes,-   b) propellant in a total amount of 0 to 99 wt %, with respect to the    total weight of the antiperspirant cosmetic agent, and-   c) at least one chitosan having a viscosity of 15 to 15,000 mPa*s,    wherein the chitosan has the formula (I),

whereinx and z, independently of each other, represent integers from 5 to25,000,y represents integers from 1 to 25,000,R represents an NH₂ group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃⁺OHCH₂C(O)O⁻,with the stipulation that the sequence of the units included in thesquare brackets and having the indices x, y, and z can be freely chosenand the residue R is bonded by means of *, and

-   d) no aluminum-containing compounds,    to reduce and/or prevent perspiration, particularly underarm    perspiration or perspiration of other body regions.

A non-therapeutic cosmetic method for preventing and/or reducing theperspiration of the body, wherein an antiperspirant cosmetic agentaccording to one of points 1 to 10 or the cosmetic agents (M1) and (M2)of the packaging unit according to point 11 are applied to the skin,particularly to the skin of the axillae, and remain on the skin of theaxillae for at least 1 hour, preferably for at least 2 hours, morepreferably for at least 4 hours, particularly for at least 6 hours.

The following examples illustrate the present invention withoutrestricting the present invention to said examples:

EXAMPLES

1. Determination of the Opacification

The determination of the opacification that is caused by the followingchitosans in a pH range of 5.5 to 7.5 in the event of a pH value changeof 0.5 is performed as follows:

TABLE 1 Sample solution (specifications in wt %) E-I* E-II* Chitosan1^(a)) 0.25 — Chitosan 2^(b)) — 0.10 Lactic acid 0.07 0.18 HCl ad pH adpH Water ad 100 ad 100 *according to the invention ^(a))R = *—NH₃⁺CH₃CH(OH)C(O)O⁻, M_(w) = 50,000 to 1,000,000 Da, viscosity = 70 to 150mPa * s, degree of deacetylation ≧80%, marine source ^(b))R = *—NH₃⁺CH₃CH(OH)C(O)O⁻, M_(w) = 10,000 to 20,000 Da, viscosity = 20 to 40mPa * s, degree of deacetylation ≧80%, plant source

For the determination of the opacification, a Methrom Titrando 905 fromthe company Methrom (USA) was used, which is equipped with a MethromOptrode 6.1115.000 and a pH electrode from Methrom. The Methrom Titrando905 is controlled by means of the Tiamo software from Methrom. First, 30ml of a sample solution according to table 1, which had a pH value of3.0, was provided in the open sample vessel of the Methrom Titrando 905.Then, at 23° C. and 1,013 mbar and while stirring (stirring speed 8 ofthe Titrando 905), a 1 wt % sodium hydrogen carbonate solution was addedcontinuously until a pH value of 7.5 was reached. During the addition ofthe 1 wt % sodium hydrogen carbonate solution, the light transmission ofa light beam through said sample solution was measured in mV (resolutionof 0.1 mV) at a wavelength of 574 nm (greenish yellow) by using aMethrom Optrode 6.1115.000. Each measurement is performed twice and themean is calculated therefrom.

The opacification, or change in the light absorption, that was caused bythe aforementioned chitosans was determined in accordance with theformula ΔL=[(|L_(i)|/|L₀|]*100. In this formula, L_(i) represents thedifference of the light transmission before and after a change in the pHvalue by at least 0.5 in the pH range of 4.0 to 8.0, preferably pH 4.5and 7.5, particularly pH 5.0 and 7.0. In this formula, L₀ represents thedifference of the light transmission at pH 4.0 and at pH 8.0, preferablyat pH 4.5 and at pH 7.5, particularly at pH 5.0 and at pH 7.0.

In the event of a pH value change of 0.5 between pH 6.0 and pH 6.5(difference of light absorption at pH 6.5 minus light absorption at pH6.0 forms the value L_(i)) in a pH value range of 5.5 to 7.5 (differenceof light absorption at pH 7.5 minus light absorption at pH 5.5 forms thevalue L₀), said chitosans caused the change in the light absorption ΔL,or opacification, indicated in table 2.

TABLE 2 Change in the light absorption ΔL, or opacification Samplesolution ΔL [%] E-I (chitosan 1) 30 E-II (chitosan 2) 4

2. Formulations:

The following chitosans of formula (I) are preferably used in theexamples below:

-   -   R=*—NH₃ ⁺CH₃CH(OH)C(O)O⁻, M_(w)=50,000 to 1,000,000 Da,        viscosity=70 to 150 mPa*s, degree of deacetylation ≧80%, marine        source    -   R=*—NH₃ ⁺CH₃CH(OH)C(O)O⁻, M_(w)=50,000 to 1,000,000 Da,        viscosity=1,000 to 5,000 mPa*s, degree of deacetylation ≧80%,        marine source    -   R=*—NH₃ ⁺OHCH₂C(O)O⁻, M_(w)=500,000 to 5,000,000 Da,        viscosity=500 to 5,000 mPa*s, degree of deacetylation ≧80%,        marine source    -   R═NH₂ group, M_(w)=300,000 to 2,000,000 Da, viscosity=150 to        1,000 mPa*s, degree of deacetylation ≧80%, marine source    -   R═NH₂ group, M_(w)=50,000 to 5,000,000 Da, viscosity=1,850 to        2,250 mPa*s, degree of deacetylation ≧80%, marine source    -   R=*—NH₃ ⁺CH₃CH(OH)C(O)O⁻, M_(w)=10,000 to 20,000 Da,        viscosity=20 to 40 mPa*s, degree of deacetylation ≧80%, plant        source

Antiperspirant cosmetic agents according to the invention having a pH of2.5 to 6.0 (amount specifications in wt %)

1 2 3 4 5 6 7 Isopropyl myristate 0.50 0.10 0.50 1.0 2.0 3.0 5.0Chitosan of formula (I) 0.05 0.1 0.2 0.3 0.4 1.5 2.0 Eumulgin B3^(a) 3.03.0 3.0 4.0 4.0 4.0 5.0 Perfume 0.10 0.20 0.30 0.30 0.30 0.30 0.30Preservative agent 0.50 0.50 0.50 0.80 0.80 1.5 2.0 pH adjuster ad pH adpH ad pH ad pH ad pH ad pH ad pH Water ad 100 ad 100 ad 100 ad 100 ad100 ad 100 ad 100 ^(a)Eumulgin B3 (INCI: Ceteareth-30; BASF)

Antiperspirant cosmetic agents according to the invention having a pH of2.5 to 6.0, in the form of sprayable emulsions (amount specifications inwt %)

1 2 3 4 Cyclopentasiloxane 11 11 13 15 Isopropyl myristate 5.0 5.0 5.05.0 Dow Corning ES-5227 DM^(b)) 6.0 6.0 7.0 7.0 Perfume 4.0 4.0 5.0 4.0Propylene glycol 20 20.5 18 15 Phenoxyethanol 0.5 0.5 0.5 0.5 Sodiumbenzoate 0.4 0.4 0.4 0.4 Chitosan of formula (I) 1.0 0.5 2.0 0.5Hydrochloric acid, 20% ad pH ad pH ad pH ad pH Water ad 100 ad 100 ad100 ad 100 ^(b))Dow Corning ES-5227 (INCI: Dimethicone, PEG/PPG-18/18Dimethicone; Dow Corning)

Antiperspirant cosmetic agents according to the invention having a pH of2.5 to 6.0, in the form of roll-ons (amount specifications in wt %)

1 2 3 4 Steareth-21 1.5 1.5 2.0 2.0 Steareth-2 2.5 2.5 3.0 2.0 PPG-15stearyl ether 0.5 0.5 1.0 0.5 Perfume 1.0 1.0 1.5 1.0 Tetrasodium EDTA0.1 0.1 0.1 0.1 Chitosan of formula (I) 1.0 0.5 2.0 0.5 Hydrochloricacid, 20% ad pH ad pH ad pH ad pH Water ad 100 ad 100 ad 100 ad 100

While at least one exemplary embodiment has been presented in theforegoing detailed description of the invention, it should beappreciated that a vast number of variations exist. It should also beappreciated that the exemplary embodiment or exemplary embodiments areonly examples, and are not intended to limit the scope, applicability,or configuration of the invention in any way. Rather, the foregoingdetailed description will provide those skilled in the art with aconvenient road map for implementing an exemplary embodiment of theinvention, it being understood that various changes may be made in thefunction and arrangement of elements described in an exemplaryembodiment without departing from the scope of the invention as setforth in the appended claims and their legal equivalents.

What is claimed is:
 1. An antiperspirant cosmetic agent, comprising: a)at least one substance selected from the group consisting of: cosmeticoils that are liquid at 20° C. and 1,013 hPa, odorous substances, andwaxes, b) propellant in a total amount of 0 to 99 wt %, with respect tothe total weight of the antiperspirant cosmetic agent, and c) at leastone chitosan having a viscosity of 15 to 15,000 mPa*s, wherein thechitosan has the formula (I),

wherein x and z, independently of each other, represent integers from 5to 25,000, y represents integers from 1 to 25,000, R represents an NH₂group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃ ⁺OHCH₂C(O)O⁻, with thestipulation that the sequence of the units contained in the squarebrackets and having the indices x, y, and z can be freely chosen and theresidue R is bonded by means of *, and d) no aluminum-containingcompounds.
 2. The antiperspirant cosmetic agent according to claim 1,wherein y represents integers from 1 to 22,000 in formula (I).
 3. Theantiperspirant cosmetic agent according to claim 1, wherein y representsintegers, from 1 to 17,500, in formula (I).
 4. The antiperspirantcosmetic agent according to claim 1, wherein x and z, independently ofeach other, represent integers from 5 to 20,000 in formula (I).
 5. Theantiperspirant cosmetic agent according to claim 1, wherein x and z,independently of each other, represent integers from 10 to 11,700, informula (I).
 6. The antiperspirant cosmetic agent according to claim 1,wherein the at least one chitosan of formula (I) has a degree ofdeacetylation of 70 to 99%.
 7. The antiperspirant cosmetic agentaccording to claim 1, wherein the at least one chitosan of formula (I)has a degree of deacetylation of 80 to 90%.
 8. The antiperspirantcosmetic agent according to claim 1, wherein the at least one chitosanof formula (I) has a viscosity of 15 to 10,000 mPa*s wherein theviscosity is determined by means of a Brookfield RVDV II+, spindle no.2, at 20 rpm and at 20° C., and wherein 1 wt % of chitosan of formula(I) in a 1 wt % acetic acid solution, with respect to the total weightof the solution, is used to determine the viscosity.
 9. Theantiperspirant cosmetic agent according to claim 1, wherein the at leastone chitosan of formula (I) has a viscosity of 15 to 5,000 mPa*s whereinthe viscosity is determined by means of a Brookfield RVDV II+, spindleno. 2, at 20 rpm and at 20° C., and wherein 1 wt % of chitosan offormula (I) in a 1 wt % acetic acid solution, with respect to the totalweight of the solution, is used to determine the viscosity.
 10. Theantiperspirant cosmetic agent according to claim 1, wherein the at leastone chitosan of formula (I) is included in a total amount of 0.05 to 40wt % with respect to the total weight of the propellant-freeantiperspirant cosmetic agent.
 11. The antiperspirant cosmetic agentaccording to claim 1, wherein the at least one chitosan of formula (I)is included in a total amount of 0.5 to 20 wt % with respect to thetotal weight of the propellant-free antiperspirant cosmetic agent. 12.The antiperspirant cosmetic agent according to claim 1, wherein the atleast one chitosan of formula (I) is included in a total amount of 0.2to 30 wt % with respect to the total weight of the propellant-freeantiperspirant cosmetic agent.
 13. A packaging unit (kit of parts),comprising—produced separate from each other— a) at least one firstcontainer (C1), containing a cosmetic agent (M1) comprising at least oneantiperspirant active substance, and b) at least one second container(C2), containing a cosmetic agent (M2) comprising at least one chitosanof formula (I),

wherein x and z, independently of each other, represent integers from 5to 25,000, y represents integers from 1 to 25,000, R represents an NH₂group or *—NH₃ ⁺CH₃CH(OH)C(O)O⁻ or *—NH₃ ⁺OHCH₂C(O)O⁻, with thestipulation that the sequence of the units contained in the squarebrackets and having the indices x, y, and z can be freely chosen and theresidue R is bonded by means of *, and wherein the cosmetic agent (M2)includes no aluminum-containing compounds.
 14. A method for preventingand/or reducing the perspiration of the body, comprising applying theantiperspirant cosmetic agent to a skin of the axillae and leaving thecosmetic agent on the skin for at least 1 hour. according to claim 1particularly to the skin of the axillae, and remain on the skin of theaxillae for at least 1 hour, preferably for at least 2 hours, morepreferably for at least 4 hours, particularly for at least 6 hours.